Treating hydrocarbon oils



July 19, 1932. F. w. HALL E'r AL TREATING HYDROCARBON OILS Filed July 9, 1928 III lsbl

mbt $59 Patented July 19, 1932 UNITED STATES PATENT QFICE,

EEANE w; HALL, E PORT AETHUE, TEXAS, AND vANcE N. JENKINS, DE ELIZABETH,

NEW JERSEY, AsSIGNoEs To THE TEXAS COMPANY, 0E NEW-YORK, N. Y., A coEPoEA- TION OF DELAWARE TEEATING HYDEooAEBoN OILS Applicaties med July 9, 1928K. serial No. 291,202. l

This invention relates to treating hydrocarbon oils yand more particularly to the conversion of higher 'boiling hydrocarbon 011 into lower boiling oils through the action of an aluminum chlorid catalyst at elevated temperatures. y y i y Broadlythe invention comprises a process wherein a body of oil is maintained under conditions of distillation, the vapors evolved therefrom condensed to form( a hot condensate and contacted with an aluminum chlorid catalystwhereby a portion thereof is con verted into lower boiling o il passing 0E as vapor, the unconverted portion of the .oil

s being returned to the still. The conversion may be carried on at atmospheric pressure o r under supc iatmosphericl pressure.'

In'one form of` the'invention the higher boiling oil vto undergo conversion @may be y charged directly in contact with the oil vapors vevolved from'thebody ofoil undergoing distillation, whereby the vapors are condensed and the oil charge heated to form a hot mixture 'of oil charge and condensate version by contact with an aluminum chlorid catalyst. l Y y i Animportant feature ofthe invention is Vthe'method of contacting the aluminum chlorid catalystand heated oil without bringing the catalyst into contact with'the externally Y heated surfaces of the apparatus. The

method has the added advantagethat'relatively non-volatile, ta-rryfproducts ofthe conversionreaction do not` come in contact with the fresh orlactive catalyst, thereby promoting longer `'life and greater efficiency in the catalyst.` 0l f r1`he invention may be readily understood vprocessconsidered in connection with the accompanying drawing which represents a somewhat diagrammatic sectional; 'elevation of apparatus withinrthe invention 'and suitwhich is thereafter caused to undergo coni Ytact section 19 of the tower 18.`

able Vfor usein carrying on the conversion process.

Referring to the" drawing, there i*is ypro-v vided a charging pump 11 for the purpose of forcing the oil charge from a `suitable source. (not shown) through the charging line 12 tothe still 13. The still 13, which maybe of the vertical type,` as shown, is provided with'suitable heating means such as the surrounding furnace 14. Electrical or other suitable heating means may beprovided if desired, -Adraw-off connection V15, fitted with the valve 16, is .provided atthe lower end of the still, while a vaporil'ine, 17 leads `from the vapor space inthe upper portion of the still to the tower 18. i i

` The tower 18 is divided into two sections, the lower or contact section 19 being provided with suitable vbaffles 2() and at its lower ond a line 21 leading to thE lOvver portionof the still 13, preferably below the heated portion ofthe still. Thefline 21 is tte'dfwith valves 22l and 23 and a branch line 211,- as shown.' v A.

Asuitable source lof catalyst material (not shown) is connected to the catalystA pump 25,v

which is in turn connected through the line 26, fitted with the valve 27, to the distributer 28, placedfln the upper portion ofthe con- A@Illieu'pper or fractionating portion 29 of the tower'18 may: be :of any suitable construction'such for'example as a packed tower, or

of the type'knownas abubble tower. AP

connection 30 is'provided at the upper end of the tower 29 and'is fitted with a valve y31 and a distributer 32 within ythe tower whereby liquid refiux material maybe introduced directly into the upper portionofgthetower.

.Other suitable means fo'rycooln thy from a description of the procedureof the `1 g e upper `enters the towerr29 at its upper end, being fitted withrthe valve 34 and distributer '35 p whereby the chagfdesired, may be intro-V .A suitable oil for conversion, which will bel referred to as the charging stock and which may be a kerosene or gas oil fraction of petroleum or other suitable material, is forced by means of the charging pump 11 through sectionof the tower.v

the charging line 12 tothestill 13,'k the valve 42 v,being open while the valve 34 is closed. If desired, the oil charge' may be heated by suitable means (not shown) before introduction into the still. The still 13 is heatedby means of the furnace 14 to a temperature 'suitable for vaporizing the oil charge, The temperature of the contents of thestill will vary'somewhat depending upon the pressure maintained and also upon the characteristics of the oil charge, but in the case of a light gas oil charge and operations under normal atmospfheric pressure, the temperature in the still may be substantially 540O F.

The charge `is'vaporized'and distilled from the still 13 through the vapor line 17 into the "tower iS'at a Vpoint approximately at 'the dividing line between the contact section 19 Iand the fr'actionat'ing section 29'of thetower. The oil vapors then pass upward through fthe fractionating section 2.9 but are cooled by means of theliquid reiiur material entering thel tower through the line 30 and distributed therein through theA distributer V32. y Accordingly the vapors of the charge oil are con- Y densed, running back into the contact secgtion 19 of the tower 18.' In the centact'section 19 the aluminum Vchlorid catalyst, preferably in the form of liquid aluminum chloridhydrocarbon compound, is introduced through the line 2G into `the distributer 28 by means ofthe catalyst pump 25. rl`he liquid catalyst and the hot `condensate from the fractionating section 29 of the tower 18, flow downward through the contact section 19 of the tower over the baffles 20 thereby coming in intimate contact and, being at elevated temperatures which may be in the neighborhooc'l of 500o F. or more` the conversion reaction takes place in this As the conversion reaction takes place the lighter products ofthe reaction are Vvapori'zed and pass upward through the fractionating sectionY 29, beingsubj'ected therein to fractional distillation whereby they are sep- Vara'ted from theheavier products of the reaction and the less volatile charging oil. The degree of fractionation obtained and the boiling range of the distillate may be varied by varying the amount of reflux material admitted to the tower through the connection at 30, by means of the manipulation of the valve 31. Preferably, the operation'is so carried on that the vapors leaving the tower 29 through the vapor line 36 to the condenser 37 may be of a boiling range substantially equal to that of ordinary gasoline. The condensable portion of the vapors is condensed .in the condenser 37 and, together with-non condensablegases, passes through the line 38 to the receiving drum 39 where the condensate may be withdrawn through theconnection at 41, while fixed gases may be withdrawn through the connection at 40.

In-the lower portion of the contact section 19, the heavier and less volatile portion of the convertedv oil collects, together with the unconverted oil Aand the spentcata'lyst. This mixture flows from the contact section 19 through the line 21 and may lbe withdrawn through the connection at 24 'by means of the valve 23, but preferably, the valvev 23 is maintained closed while the valve 22 is opened and the mixture of spent catalyst.,"unc`on4 verted charging stock, and the heavier products of' the conversion reaction,`flow` to the lowerportion of the still 13, t-heniixture Vpreferably entering the still at. a point' below that at which heat is applied. In the still the spent catalyst tends to settle to the bottom as do also the heaviest ofthe products of conversion, while the unconverted oil is Vagain vaporized and, passing through the vapor line 17, is again subjected to the action of the catalyst. The material settling to the bottom of the still 13 may be withdrawn c'ontinuously or periodically through the con'- nection at 15 by means of the valve 16.

In a modified method of operation, the valve 4 2 may be closed and the valve 34Y open-ed wherebyY the oil chargeis forced by means of the pump l1 through the line 33 into the fractionating section 29 of the tower 18, being distributed therein byvmeans of the fdistributer35. By this' means the coolI` vcharge meets the ascending vapors'from the' still 13 a-ndisv heated thereby, thereafter assing through .the contact section 19 o Vv'the tower 18 wher-ein it comes-in contact with the catalyst and issubjected to the actionof' the catalyst. If desired, varying portions of -the charge may be thus introduced into the tower, the remaining portion being intro duced into Vthe still through the line' 12, asirst described. In suchv operation, vthe cool' charge may serve to supply a portion or all of the reiiux tcooling applied to the tower and the quantity of cooling supplied through the connection 30 may be modified accordmethodof operation in which thel oil Vis iningly. A vparticular A advantage of*Ak the` troduced into the fractionating section 29 is that by this means the charge thus introduced is thoroughly dehydrated before it is possible for it to come in contact with the aluminum chlorid catalyst, the activity of which is completely destroyed by moisture.

The process mayl be carried on under superatmospheric pressure if desired. For example, in the conversion of a comparatively low boiling oil which may be of the nature of a light kerosene distillate, to form a material boiling within the .ordinary gasoline range, it may be found that the temperature of the oil in the contactsection 19y will not be high enough to cause the.l conversion reaction to take place readily Vin the presence of the catalyst. Under such conditions a superatmospheric pressure may be maintained upon the entire apparatus. whereby the oil in the still 13 will boil'atahigher temperature. By such means the temperature of the hot condensate flowing into the contact section 19 from the fractionating section 29 will be materially increased thereby increasing the speed of the conversion reaction as desired.

Obviously many modications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof, and therefore, only such limitations should be imposed as Y are indicated in the appended claims.

We claim:

1. The process of converting higher boiling hydrocarbon oil into lower boiling oil which comprises maintaining a body of oil under conditions of distillation, passing evolved vapors into a fractionating tower, continuously introducing fresh oil into the tower whereby a portion or all of the vapors are condensed and the fresh oil heated, contacting said condensate and fresh oil with an aluminum chlorid catalyst while maintained at a conversion temperature, separate from said body of oil undergoing distillation and not in direct contact with said vapors evolved from said body of oil, whereby a portion of the condensate is `converted into lower boilingoil, passing vapors of said lowerboiling oil through said fractionating tower and returningrthe unconverted portion of the oil to the said body of oil undergoing distillation.

2. The process of converting higher boiling hydrocarbon oil into lower boiling oil which comprises maintaining a body of oil under conditions of distillation; passing evolved vapors into Va fractionating tower,`

continuously introducing fresh oilginto the maintained at a conversion temperature,

fractionating tower whereby a portion or all of the vapors are condensed and the fresh oil heated, passing the mixture of condensate and fresh oil through a contact zonetogether with an aluminum chlorid catalyst while 

